Aqueous binder compositions

ABSTRACT

An aqueous binder composition is disclosed that comprises at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 Daltons; a primary cross-linking agent comprising at least two carboxylic acid groups; and a secondary cross-linking agent comprising a short-chain polyol having at least two hydroxyl groups and a number average molecular weight less than 2,000 Daltons.

RELATED APPLICATIONS

This application is a continuation of U.S. Non-Provisional patentapplication Ser. No. 16/154,794, filed Oct. 9, 2018, which claimspriority to and any benefit of U.S. Provisional Patent Application No.62/569,778, filed Oct. 9, 2017, the entire contents of which areincorporated herein by reference.

BACKGROUND

Aqueous binder compositions are traditionally utilized in the formationof woven and non-woven fibrous products, such as insulation products,composite products, wood fiber board, and the like. Insulation products,for example fiberglass and mineral wool insulation products, aretypically manufactured by fiberizing a molten composition of polymer,glass, or other mineral and spinning fine fibers from a fiberizingapparatus, such as a rotating spinner. To form an insulation product,fibers produced by a rotating spinner are drawn downwardly from thespinner towards a conveyor by a blower. As the fibers move downward, abinder material is sprayed onto the fibers and the fibers are collectedinto a high loft, continuous blanket on the conveyor. The bindermaterial gives the insulation product resiliency for recovery afterpackaging and provides stiffness and handleability so that theinsulation product can be handled and applied as needed in theinsulation cavities of buildings. The binder composition also providesprotection to the fibers from interfilament abrasion and promotescompatibility between the individual fibers. The blanket containing thebinder-coated fibers is then passed through a curing oven and the binderis cured to set the blanket to a desired thickness.

After the binder has cured, the fiber insulation may be cut into lengthsto form individual insulation products, and the insulation products maybe packaged for shipping to customer locations.

Fiberglass insulation products prepared in this manner can be providedin various forms including batts, blankets, and boards (heated andcompressed batts) for use in different applications. As the batt ofbinder-coated fibers emerges from the forming chamber, it will tend toexpand as a result of the resiliency of the glass fibers. The expandedbatt is then typically conveyed to and through a curing oven in whichheated air is passed through the insulation product to cure the binder.In addition to curing the binder, within the curing oven, the insulationproduct may be compressed with flights or rollers to produce the desireddimensions and surface finish on the resulting blanket, batt or boardproduct.

Phenol-formaldehyde (PF) binder compositions, as well as PF resinsextended with urea (PUF resins), have been traditionally used in theproduction of fiberglass insulation products. Insulation boards, alsoknown as “heavy density” products, such as ceiling board, duct wrap,duct liners, and the like have utilized phenol-formaldehyde bindertechnology for the production of heavy density products that areinexpensive and have acceptable physical and mechanical properties.However, formaldehyde binders emit undesirable emissions during themanufacturing of the fiberglass insulation.

As an alternative to formaldehyde-based binders, certainformaldehyde-free formulations have been developed for use as a binderin fiberglass insulation products. One of the challenges to developingsuitable alternatives, however, is to identify formulations that havecomparable mechanical and physical properties, while avoidingundesirable properties, such as discoloration. Such property challengesinclude hot/humid performance, stiffness, bond strength, processability(viscosity, cutting, sanding, edge painting), and achieving a lightcolor without yellowing.

Accordingly, there is a need for an environmentally friendly,formaldehyde-free binder composition for use in the production ofinsulation products without experiencing a loss in physical andmechanical properties.

SUMMARY

Various exemplary aspects of the inventive concepts are directed to anaqueous binder composition comprising at least one long-chain polyolhaving at least two hydroxyl groups and a number average molecularweight of at least 2,000; a cross-linking agent comprising at least twocarboxylic acid groups; and a short-chain polyol having at least twohydroxyl groups and a number average molecular weight less than 2,000,wherein a ratio of molar equivalents of carboxylic acid groups tohydroxyl groups is from about 1/0.05 to about 1.0/5.0 and a ratio oflong-chain polyol to short-chain polyol is from about 0.1/0.9 to about0.9/0.1.

In some exemplary embodiments, the cross-linking agent is a polymericpolycarboxylic acid, such as a homopolymer of copolymer of acrylic acid.The cross-linking agent may be present in the binder composition in anamount from about 50 wt. % to about 85 wt. %, based on the total solidscontent of the aqueous binder composition. In some exemplaryembodiments, the cross-linking agent is present in the bindercomposition in an amount from about 65 wt. % to about 80 wt. %, based onthe total solids content of the aqueous binder composition.

In some exemplary embodiments, the long-chain polyol is selected fromthe group consisting of partially or fully hydrolyzed polyvinyl alcoholand polyvinyl acetate. The long-chain polyol may be present in thebinder composition in an amount from about 5 wt. % to about 30 wt. %,based on the total solids content of the aqueous binder composition. Invarious exemplary embodiments, the short-chain polyol comprises one ormore of a sugar alcohol, 2,2-bis(methylol)propionic acid,tri(methylol)propane, and a short-chain alkanolamine. When theshort-chain polyol comprises a sugar alcohol, the sugar alcohol may beselected from the group consisting of glycerol, erythritol, arabitol,xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol,cellobitol, palatinitol, maltotritol, syrups thereof, and mixturesthereof.

In various exemplary embodiments, the short-chain polyol is present inthe binder composition in an amount from about 3 wt. % to about 30 wt.%, based on the total solids content of the aqueous binder composition.

In various exemplary embodiments, the binder composition has awater-soluble material content after cure of no greater than 6.0 wt. %.

Other exemplary aspects of the inventive concepts are directed to aninsulation product comprising a plurality of randomly oriented fibersand an aqueous binder composition at least partially coating the fibers.The binder composition may comprise at least one long-chain polyolhaving at least two hydroxyl groups and a number average molecularweight of at least 2,000 Daltons; a cross-linking agent comprising atleast two carboxylic acid groups; and a short-chain polyol having atleast two hydroxyl groups and a number average molecular weight lessthan 2,000 Daltons. In some exemplary embodiments, the ratio of molarequivalents of carboxylic acid groups to hydroxyl groups is from about1/0.05 to about 1.0/5.0 and the ratio of long-chain polyol toshort-chain polyol is from about 0.1/0.9 to about 0.9/0.1.

The fibers of the insulation products may comprise one or more ofmineral fibers, natural fibers, and synthetic fibers, and in someembodiments, the fibers comprise glass fibers.

Numerous other aspects, advantages, and/or features of the generalinventive concepts will become more readily apparent from the followingdetailed description of exemplary embodiments and from the accompanyingdrawings being submitted herewith.

BRIEF DESCRIPTION OF THE DRAWINGS

The general inventive concepts, as well as illustrative embodiments andadvantages thereof, are described below in greater detail, by way ofexample, with reference to the drawings in which:

FIG. 1 graphically illustrates the flexural stress/wt./LOI forfiberglass insulation made with exemplary cured binder compositionshaving varying ratios of molar equivalent carboxylic acidgroups/hydroxyl groups and long-chain polyol/short-chain polyol.

FIG. 2 graphically illustrates the tensile force/LOI for fiberglass madewith exemplary binder compositions having a ratio of molar equivalentcarboxylic acid groups/hydroxyl groups of 1/0.1 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 3 graphically illustrates the % water soluble material post-curefor exemplary binder compositions having a ratio of molar equivalentcarboxylic acid groups/hydroxyl groups of 1/0.1 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 4 graphically illustrates the tensile force/LOI for exemplary curedbinder compositions having a ratio of molar equivalent carboxylic acidgroups/hydroxyl groups of 1/1.5 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 5 graphically illustrates the % water soluble material post-curefor exemplary binder compositions having a ratio of molar equivalentcarboxylic acid groups/hydroxyl groups of 1/1.5 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 6 graphically illustrates the tensile force/LOI for exemplary curedbinder compositions having a ratio of molar equivalent carboxylic acidgroups/hydroxyl groups of 1/0.5 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 7 graphically illustrates the % water soluble material post-curefor exemplary binder compositions having a ratio of molar equivalentcarboxylic acid groups/hydroxyl groups of 1/0.5 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 8 graphically illustrates the tensile force/LOI for exemplary curedbinder compositions having a ratio of molar equivalent carboxylic acidgroups/hydroxyl groups of 1/0.1 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 9 graphically illustrates the % water soluble material post-curefor exemplary binder compositions having a ratio of molar equivalentcarboxylic acid groups/hydroxyl groups of 1/1 and varying long-chainpolyol/short-chain polyol ratios.

FIG. 10 graphically illustrates the tensile force/LOI for exemplarycured binder compositions having varied ratios of molar equivalentcarboxylic acid groups/hydroxyl groups.

FIG. 11 graphically illustrates the flexural elastic modulus for planttrial boards formed using various binder compositions in accordance withthe subject application, compared to conventional starch-hybrid bindercompositions and phenol urea formaldehyde-based binder compositions.

FIG. 12 graphically illustrates the sag for 4′×4′ fiberglass insulationceiling board tiles formed using various binder compositions inaccordance with the subject application, compared to conventionalstarch-hybrid binder compositions and phenol urea formaldehyde-basedbinder compositions under hot/humid conditions.

FIG. 13 graphically illustrates the compressive strength of plant trialboard products, formed using various binder compositions in accordancewith the subject application, compared to conventional starch-hybridbinder compositions and phenol urea formaldehyde-based bindercompositions.

FIG. 14 graphically illustrates the bond strength at break of planttrial board products formed using various binder compositions inaccordance with the subject application, compared to conventionalstarch-hybrid binder compositions and phenol urea formaldehyde-basedbinder compositions.

DETAILED DESCRIPTION

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which these exemplary embodiments belong. The terminologyused in the description herein is for describing exemplary embodimentsonly and is not intended to be limiting of the exemplary embodiments.Accordingly, the general inventive concepts are not intended to belimited to the specific embodiments illustrated herein. Although othermethods and materials similar or equivalent to those described hereincan be used in the practice or testing of the present invention, thepreferred methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” are intended to include the plural forms as well,unless the context clearly indicates otherwise.

Unless otherwise indicated, all numbers expressing quantities ofingredients, chemical and molecular properties, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thespecification and attached claims are approximations that may varydepending upon the desired properties sought to be obtained by thepresent exemplary embodiments. At the very least each numericalparameter should be construed in light of the number of significantdigits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the exemplary embodiments are approximations, thenumerical values set forth in the specific examples are reported asprecisely as possible. Any numerical value, however, inherently containscertain errors necessarily resulting from the standard deviation foundin their respective testing measurements. Every numerical range giventhroughout this specification and claims will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

The present disclosure relates to formaldehyde-free aqueous bindercompositions for use in the manufacture of insulation products that havecomparable or improved mechanical and physical performance, compared toproducts manufactured with traditional formaldehyde-based bindercompositions. The formaldehyde-free binder composition may be used inthe manufacture of fiber insulation products and related products, suchas thin fiber-reinforced mats (all hereinafter referred to genericallyas fiber reinforced products) and glass fiber or mineral wool products,especially fiberglass or mineral wool insulation products, made with thecured formaldehyde-free binder. Other products may include compositeproducts, wood fiber board products, metal building insulation, pipeinsulation, ceiling board, ceiling tile, “heavy density” products, suchas ceiling board, duct wrap, duct liners, and also “light density”products.

In some exemplary embodiments, the formaldehyde-free aqueous bindercomposition includes at least one long-chain polyol, and at least oneprimary cross-linking agent, and at least one secondary cross-linkingagent comprising at least one short-chain polyol.

The primary crosslinking agent may be any compound suitable forcrosslinking the polyol. In exemplary embodiments, the primarycrosslinking agent has a number average molecular weight greater than 90Daltons, from about 90 Daltons to about 10,000 Daltons, or from about190 Daltons to about 5,000 Daltons. In some exemplary embodiments, thecrosslinking agent has a number average molecular weight of about 2,000Daltons to 5,000 Daltons, or about 4,000 Daltons. Non-limiting examplesof suitable crosslinking agents include materials having one or morecarboxylic acid groups (—COOH), such as polycarboxylic acids (and saltsthereof), anhydrides, monomeric and polymeric polycarboxylic acid withanhydride (i.e., mixed anhydrides), and homopolymer or copolymer ofacrylic acid, such as polyacrylic acid (and salts thereof) andpolyacrylic acid based resins such as QR-1629S and Acumer 9932, bothcommercially available from The Dow Chemical Company. Acumer 9932 is apolyacrylic acid/sodium hypophosphite resin having a molecular weight ofabout 4000 and a sodium hypophosphite content of 6-7% by weight.QR-1629S is a polyacrylic acid/glycerin mixture.

The primary cross-linking agent may, in some instances, bepre-neutralized with a neutralization agent. Such neutralization agentsmay include organic and/or inorganic bases, such sodium hydroxide,ammonium hydroxide, and diethylamine, and any kind of primary,secondary, or tertiary amine (including alkanol amine). In variousexemplary embodiments, the neutralization agents may include at leastone of sodium hydroxide and triethanolamine.

In some exemplary embodiments, the primary crosslinking agent is presentin the aqueous binder composition in at least 50 wt. %, based on thetotal solids content of the aqueous binder composition, including,without limitation at least 55 wt. %, at least 60 wt. %, at least 63 wt.%, at least 65 wt. %, at least 70 wt. %, at least 73 wt. %, at least 75wt. %, at least 78 wt. %, and at least 80 wt. %. In some exemplaryembodiments, the primary crosslinking agent is present in the aqueousbinder composition in an amount from 50% to 85% by weight, based on thetotal solids content of the aqueous binder composition, includingwithout limitation 60% to 80% by weight, 62% to 78% by weight, and 65%to 75% by weight.

In some exemplary embodiments, the long-chain polyol comprises a polyolhaving at least two hydroxyl groups having a number average molecularweight of at least 2,000 Daltons, such as a molecular weight between3,000 Daltons and 4,000 Daltons. In some exemplary embodiments, thelong-chain polyol comprises one or more of a polymeric polyhydroxycompound, such as a polyvinyl alcohol, polyvinyl acetate, which may bepartially or fully hydrolyzed, or mixtures thereof. Illustratively, whena partially hydrolyzed polyvinyl acetate serves as the polyhydroxycomponent, an 80%-89% hydrolyzed polyvinyl acetate may be utilized, suchas, for example Poval® 385 (Kuraray America, Inc.) and Sevol™ 502(Sekisui Specialty Chemicals America, LLC), both of which are about 85%(Poval® 385) and 88% (Selvol™ 502) hydrolyzed.

The long-chain polyol may be present in the aqueous binder compositionin an amount up to about 30% by weight total solids, including withoutlimitation, up to about 28%, 25%, 20%, 18%, 15%, and 13% by weight totalsolids. In some exemplary embodiments, the long-chain polyol is presentin the aqueous binder composition in an amount from 5.0% to 30% byweight total solids, including without limitation 7% to 25%, 8% to 20%,9% to 18%, and 10% to 16%, by weight total solids.

Optionally, the aqueous binder composition includes a secondarycrosslinking agent, such as a short-chain polyol. The short-chain polyolmay comprise a water-soluble compound having a molecular weight of lessthan 2,000 Daltons, including less than 750 Daltons, less than 500Daltons and having a plurality of hydroxyl (—OH) groups. Suitableshort-chain polyol components include sugar alcohols,2,2-bis(methylol)propionic acid (bis-MPA), tri(methylol)propane (TMP),and short-chain alkanolamines, such as triethanolamine. In someexemplary embodiments, the short-chain polyol serves as a viscosityreducing agent, which breaks down the intra and inter molecular hydrogenbonds between the long-chain polyol molecules (e.g., polyvinyl alcohol)and thus lowers the viscosity of the composition. However, as thesesmall-chain polyol molecules have similar structures to the long-chainpolyols, they can react similarly with cross-linking agents, thus theydo not negatively impact the binder and product performance.

Sugar alcohol is understood to mean compounds obtained when the aldo orketo groups of a sugar are reduced (e.g. by hydrogenation) to thecorresponding hydroxy groups. The starting sugar might be chosen frommonosaccharides, oligosaccharides, and polysaccharides, and mixtures ofthose products, such as syrups, molasses and starch hydrolyzates. Thestarting sugar also could be a dehydrated form of a sugar. Althoughsugar alcohols closely resemble the corresponding starting sugars, theyare not sugars. Thus, for instance, sugar alcohols have no reducingability, and cannot participate in the Maillard reaction typical ofreducing sugars. In some exemplary embodiments, the sugar alcoholincludes glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol,mannitol, iditol, isomaltitol, lactitol, cellobitol, palatinitol,maltotritol, syrups thereof and mixtures thereof. In various exemplaryembodiments, the sugar alcohol is selected from glycerol, sorbitol,xylitol, and mixtures thereof. In some exemplary embodiments, thesecondary cross-linking agent is a dimeric or oligomeric condensationproduct of a sugar alcohol. In various exemplary embodiments, thecondensation product of a sugar alcohol is isosorbide. In some exemplaryembodiments, the sugar alcohol is a diol or glycol.

In some exemplary embodiments, the short-chain polyol is present in theaqueous binder composition in an amount up to about 30% by weight totalsolids, including without limitation, up to about 25%, 20%, 18%, 15%,13%, 11%, and 10% by weight total solids. In some exemplary embodiments,the short-chain polyol is present in the aqueous binder composition inan amount from 0 to 30% by weight total solids, including withoutlimitation 2% to 30%, 3% to 25%, 5% to 20%, 8% to 18%, and 9% to 15%, byweight total solids.

In various exemplary embodiments, the long-chain polyol, crosslinkingagent, and small-chain polyol are present in amounts such that the ratioof the number of molar equivalents of carboxylic acid groups, anhydridegroups, or salts thereof to the number of molar equivalents of hydroxylgroups is from about 1/0.05 to about 1/5, such as from about 1/0.08 toabout 1/2.0, from about 1/0.1 to about 1/1.5, and about 1/0.3 to about1/0.66. It has surprisingly been discovered, however, that within thisratio, the ratio of long-chain polyol to short-chain polyol effects theperformance of the binder composition, such as the tensile strength andwater solubility of the binder after cure. For instance, it has beendiscovered that a ratio of long-chain polyol to short-chain polyolbetween about 0.1/0.9 to about 0.9/0.1, such as between about 0.3/0.7and 0.7/0.3, or between about 0.4/0.6 and 0.6/0.4 provides a balance ofdesirable mechanical and physical properties. In various exemplaryembodiments, the ratio of long-chain polyol to short-chain polyol isapproximately 0.5/0.5. The ratio of long-chain polyol to short-chainpolyol may be optimized such that particular properties are optimized,depending on the needs of an end-use application. For instance, loweringthe long-chain polyol concentration may decrease the tensile strength ofa product formed with the binder composition. However, lowering thelong-chain polyol may affect other properties, such as physicalproperties. Thus, a balance between various properties has beenunexpectedly struck within the ratios disclosed herein.

Optionally, the aqueous binder composition may include an esterificationcatalyst, also known as a cure accelerator. The catalyst may includeinorganic salts, Lewis acids (i.e., aluminum chloride or borontrifluoride), Bronsted acids (i.e., sulfuric acid, p-toluenesulfonicacid and boric acid) organometallic complexes (i.e., lithiumcarboxylates, sodium carboxylates), and/or Lewis bases (i.e.,polyethyleneimine, diethylamine, or triethylamine). Additionally, thecatalyst may include an alkali metal salt of a phosphorous-containingorganic acid; in particular, alkali metal salts of phosphorus acid,hypophosphorus acid, or polyphosphoric. Examples of such phosphoruscatalysts include, but are not limited to, sodium hypophosphite, sodiumphosphate, potassium phosphate, disodium pyrophosphate, tetrasodiumpyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate,potassium phosphate, potassium tripolyphosphate, sodiumtrimetaphosphate, sodium tetrametaphosphate, and mixtures thereof. Inaddition, the catalyst or cure accelerator may be a fluoroboratecompound such as fluoroboric acid, sodium tetrafluoroborate, potassiumtetrafluoroborate, calcium tetrafluoroborate, magnesiumtetrafluoroborate, zinc tetrafluoroborate, ammonium tetrafluoroborate,and mixtures thereof. Further, the catalyst may be a mixture ofphosphorus and fluoroborate compounds. Other sodium salts such as,sodium sulfate, sodium nitrate, sodium carbonate may also oralternatively be used as the catalyst.

The catalyst may be present in the aqueous binder composition in anamount from about 0% to about 10% by weight of the total solids in thebinder composition, including without limitation, amounts from about 1%to about 5% by weight, or from about 2% to about 4.5% by weight, or fromabout 2.8% to about 4.0% by weight, or from about 3.0% to about 3.8% byweight.

Optionally, the aqueous binder composition may contain at least onecoupling agent. In at least one exemplary embodiment, the coupling agentis a silane coupling agent. The coupling agent(s) may be present in thebinder composition in an amount from about 0.01% to about 5% by weightof the total solids in the binder composition, from about 0.01% to about2.5% by weight, from about 0.05% to about 1.5% by weight, or from about0.1% to about 1.0% by weight.

Non-limiting examples of silane coupling agents that may be used in thebinder composition may be characterized by the functional groups alkyl,aryl, amino, epoxy, vinyl, methacryloxy, ureido, isocyanato, andmercapto. In exemplary embodiments, the silane coupling agent(s) includesilanes containing one or more nitrogen atoms that have one or morefunctional groups such as amine (primary, secondary, tertiary, andquaternary), amino, imino, amido, imido, ureido, or isocyanato.Specific, non-limiting examples of suitable silane coupling agentsinclude, but are not limited to, aminosilanes (e.g.,triethoxyaminopropylsilane; 3-aminopropyltriethoxysilane and3-aminopropyl-trihydroxysilane), epoxy trialkoxysilanes (e.g.,3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane),methyacryl trialkoxysilanes (e.g., 3-methacryloxypropyltrimethoxysilaneand 3-methacryloxypropyltriethoxysilane), hydrocarbon trialkoxysilanes,amino trihydroxysilanes, epoxy trihydroxysilanes, methacryl trihydroxysilanes, and/or hydrocarbon trihydroxysilanes. In one or more exemplaryembodiment, the silane is an aminosilane, such asγ-aminopropyltriethoxysilane.

Optionally, the aqueous binder composition may include a process aid.The process aid is not particularly limiting so long as the process aidfunctions to facilitate the processing of the fibers formation andorientation. The process aid can be used to improve binder applicationdistribution uniformity, to reduce binder viscosity, to increase rampheight after forming, to improve the vertical weight distributionuniformity, and/or to accelerate binder de-watering in both forming andoven curing process. The process aid may be present in the bindercomposition in an amount from 0 to about 10% by weight, from about 0.1%to about 5.0% by weight, or from about 0.3% to about 2.0% by weight, orfrom about 0.5% to 1.0% by weight, based on the total solids content inthe binder composition. In some exemplary embodiments, the aqueousbinder composition is substantially or completely free of any processingaids.

Examples of processing aids include defoaming agents, such as, emulsionsand/or dispersions of mineral, paraffin, or vegetable oils; dispersionsof polydimethylsiloxane (PDMS) fluids, and silica which has beenhydrophobized with polydimethylsiloxane or other materials. Furtherprocessing aids may include particles made of amide waxes such asethylenebis-stearamide (EBS) or hydrophobized silica. A further processaid that may be utilized in the binder composition is a surfactant. Oneor more surfactants may be included in the binder composition to assistin binder atomization, wetting, and interfacial adhesion.

The surfactant is not particularly limited, and includes surfactantssuch as, but not limited to, ionic surfactants (e.g., sulfate,sulfonate, phosphate, and carboxylate); sulfates (e.g., alkyl sulfates,ammonium lauryl sulfate, sodium lauryl sulfate (SDS), alkyl ethersulfates, sodium laureth sulfate, and sodium myreth sulfate); amphotericsurfactants (e.g., alkylbetaines such as lauryl-betaine); sulfonates(e.g., dioctyl sodium sulfosuccinate, perfluorooctanesulfonate,perfluorobutanesulfonate, and alkyl benzene sulfonates); phosphates(e.g., alkyl aryl ether phosphate and alkyl ether phosphate);carboxylates (e.g., alkyl carboxylates, fatty acid salts (soaps), sodiumstearate, sodium lauroyl sarcosinate, carboxylate fluorosurfactants,perfluoronanoate, and perfluorooctanoate); cationic (e.g., alkylaminesalts such as laurylamine acetate); pH dependent surfactants (primary,secondary or tertiary amines); permanently charged quaternary ammoniumcations (e.g., alkyltrimethylammonium salts, cetyl trimethylammoniumbromide, cetyl trimethylammonium chloride, cetylpyridinium chloride, andbenzethonium chloride); and zwitterionic surfactants, quaternaryammonium salts (e.g., lauryl trimethyl ammonium chloride and alkylbenzyl dimethylammonium chloride), and polyoxyethylenealkylamines.

Suitable nonionic surfactants that can be used in conjunction with thebinder composition include polyethers (e.g., ethylene oxide andpropylene oxide condensates, which include straight and branched chainalkyl and alkaryl polyethylene glycol and polypropylene glycol ethersand thioethers); alkylphenoxypoly(ethyleneoxy)ethanols having alkylgroups containing from about 7 to about 18 carbon atoms and having fromabout 4 to about 240 ethyleneoxy units (e.g.,heptylphenoxypoly(ethyleneoxy) ethanols, andnonylphenoxypoly(ethyleneoxy) ethanols); polyoxyalkylene derivatives ofhexitol including sorbitans, sorbides, mannitans, and mannides; partiallong-chain fatty acids esters (e.g., polyoxyalkylene derivatives ofsorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate);condensates of ethylene oxide with a hydrophobic base, the base beingformed by condensing propylene oxide with propylene glycol; sulfurcontaining condensates (e.g., those condensates prepared by condensingethylene oxide with higher alkyl mercaptans, such as nonyl, dodecyl, ortetradecyl mercaptan, or with alkylthiophenols where the alkyl groupcontains from about 6 to about 15 carbon atoms); ethylene oxidederivatives of long-chain carboxylic acids (e.g., lauric, myristic,palmitic, and oleic acids, such as tall oil fatty acids); ethylene oxidederivatives of long-chain alcohols (e.g., octyl, decyl, lauryl, or cetylalcohols); and ethylene oxide/propylene oxide copolymers.

In at least one exemplary embodiment, the surfactants include one ormore of Dynol 607, which is a 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol,SURFONYL® 420, SURFONYL® 440, and SURFONYL® 465, which are ethoxylated2,4,7,9-tetramethyl-5-decyn-4,7-diol surfactants (commercially availablefrom Evonik Corporation (Allentown, Pa.)), Stanfax (a sodium laurylsulfate), Surfynol 465 (an ethoxylated 2,4,7,9-tetramethyl 5decyn-4,7-diol), Triton™ GR-PG70 (1,4-bis(2-ethylhexyl) sodiumsulfosuccinate), and Triton™ CF-10 (poly(oxy-1,2-ethanediyl),alpha-(phenylmethyl)-omega-(1,1,3,3-tetramethylbutyl)phenoxy). Thebinder composition may also include organic and/or inorganic acids andbases as pH adjusters in an amount sufficient to adjust the pH to adesired level. The pH may be adjusted depending on the intendedapplication, to facilitate the compatibility of the ingredients of thebinder composition, or to function with various types of fibers. In someexemplary embodiments, the pH adjuster is utilized to adjust the pH ofthe binder composition to an acidic pH. Examples of suitable acidic pHadjusters include inorganic acids such as, but not limited to sulfuricacid, phosphoric acid and boric acid and also organic acids likep-toluenesulfonic acid, mono- or polycarboxylic acids, such as, but notlimited to, citric acid, acetic acid and anhydrides thereof, adipicacid, oxalic acid, and their corresponding salts. Also, inorganic saltsthat can be acid precursors. The acid adjusts the pH, and in someinstances, as discussed above, acts as a crosslinking agent. In otherexemplary embodiment, organic and/or inorganic bases, can be included toincrease the pH of the binder composition. In some exemplaryembodiments, the bases may be a volatile or non-volatile base. Exemplaryvolatile bases include, for example, ammonia and alkyl-substitutedamines, such as methyl amine, ethyl amine or 1-aminopropane, dimethylamine, and ethyl methyl amine. Exemplary non-volatile bases include, forexample, sodium hydroxide, potassium hydroxide, sodium carbonate, andt-butylammonium hydroxide.

When in an un-cured state, the pH of the binder composition may rangefrom about 2 to about 5, including all amounts and ranges in between. Insome exemplary embodiments, the pH of the binder composition, when in anun-cured state, is about 2.2-4.0, including about 2.5-3.8, and about2.6-3.5. After cure, the pH of the binder composition may rise to atleast a pH of 6.0, including levels between about 6.5 and 7.2, orbetween about 6.8 and 7.2.

Optionally, the binder may contain a dust suppressing agent to reduce oreliminate the presence of inorganic and/or organic particles which mayhave adverse impact in the subsequent fabrication and installation ofthe insulation materials. The dust suppressing agent can be anyconventional mineral oil, mineral oil emulsion, natural or syntheticoil, bio-based oil, or lubricant, such as, but not limited to, siliconeand silicone emulsions, polyethylene glycol, as well as any petroleum ornon-petroleum oil with a high flash point to minimize the evaporation ofthe oil inside the oven.

In some exemplary embodiments, the aqueous binder composition includesup to about 10 wt. % of a dust suppressing agent, including up to about8 wt. %, or up to about 6 wt. %. In various exemplary embodiments, theaqueous binder composition includes between 0 wt. % and 10 wt. % of adust suppressing agent, including about 1.0 wt. % to about 7.0 wt. %, orabout 1.5 wt. % to about 6.5 wt. %, or about 2.0 wt. % to about 6.0 wt.%, or about 2.5 wt. % to 5.8 wt. %.

The binder further includes water to dissolve or disperse the activesolids for application onto the reinforcement fibers. Water may be addedin an amount sufficient to dilute the aqueous binder composition to aviscosity that is suitable for its application to the reinforcementfibers and to achieve a desired solids content on the fibers. It hasbeen discovered that the present binder composition may contain a lowersolids content than traditional phenol-urea formaldehyde orcarbohydrate-based binder compositions. In particular, the bindercomposition may comprise 5% to 35% by weight of binder solids, includingwithout limitation, 10% to 30%, 12% to 20%, and 15% to 19% by weight ofbinder solids. This level of solids indicates that the subject bindercomposition may include more water than traditional binder compositions.However, due to the high cure rate of the binder composition, the bindercan be processed at a high ramp moisture level (about 8%-10%) and thebinder composition requires less moisture removal than traditionalbinder compositions. The binder content may be measured as loss onignition (LOI). In certain embodiments, LOI is 5% to 20%, includingwithout limitation, 10% to 17%, 12% to 15%, and 13% to 14.5%.

In some exemplary embodiments, the binder composition is capable ofachieving similar or higher performance than traditional phenolic orstarch-hybrid binder compositions with lower LOI.

In some exemplary embodiments, the aqueous binder composition may alsoinclude one or more additives, such as a coupling agent, an extender, acrosslinking density enhancer, a deodorant, an antioxidant, a dustsuppressing agent, a biocide, a moisture resistant agent, orcombinations thereof. Optionally, the binder may comprise, withoutlimitation, dyes, pigments, additional fillers, colorants, UVstabilizers, thermal stabilizers, anti-foaming agents, emulsifiers,preservatives (e.g., sodium benzoate), corrosion inhibitors, andmixtures thereof. Other additives may be added to the binder compositionfor the improvement of process and product performance. Such additivesinclude lubricants, wetting agents, antistatic agents, and/or waterrepellent agents. Additives may be present in the binder compositionfrom trace amounts (such as <about 0.1% by weight the bindercomposition) up to about 10% by weight of the total solids in the bindercomposition.

In some exemplary embodiments, the aqueous binder composition issubstantially free of a monomeric carboxylic acid component. Exemplarymonomeric polycarboxylic acid components include aconitic acid, adipicacid, azelaic acid, butane tetra carboxylic acid dihydrate, butanetricarboxylic acid, chlorendic anhydride, citraconic acid, citric acid,dicyclopentadiene-maleic acid adducts, diethylenetriamine pentaceticacid pentasodium salt, adducts of dipentene and maleic anhydride,endomethylenehexachlorophthalic anhydride, ethylenediamine tetraaceticacid (EDTA), fully maleated rosin, maleated tall oil fatty acids,fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleatedrosin-oxidize unsaturation with potassium peroxide to alcohol thencarboxylic acid, malic acid, maleic anhydride, mesaconic acid, oxalicacid, phthalic anhydride, polylactic acid, sebacic acid, succinic acid,tartaric acid, terephthalic acid, tetrabromophthalic anhydride,tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, trimelliticanhydride, and trimesic acid.

In various exemplary embodiments, the aqueous binder compositionincludes a long-chain polyol (e.g., fully or partially hydrolyzedpolyvinyl alcohol), a primary crosslinking agent (e.g., polymericpolycarboxylic acid), and a secondary crosslinking agent (e.g. a sugaralcohol). The range of components used in the inventive bindercomposition according to certain exemplary embodiments is set forth inTable 1.

TABLE 1 Exemplary Range 1 Exemplary Range 2 (% By Weight of (% By Weightof Component Total Solids) Total Solids) Long-chain polyol 5-30 10-20Crosslinking Agent 50-85  65-80 Short-chain polyol 3-30  5-25 Ratio ofCOOH/OH 1/0.05-1/5   1/0.3-1/2 Ratio long-chain  0.1/0.9-0.9/0.1 0.4/0.6-0.6/0.4 polyol/short-chain polyol

Aqueous binder compositions according to various exemplary embodimentsof the present disclosure may further include a catalyst/accelerator(e.g., sodium hypophosphite), a surfactant, and/or a coupling agent(e.g., silane) are set forth in Table 2.

TABLE 2 Exemplary Range 1 Exemplary Range 2 (% By Weight of (% By Weightof Component Total Solids) Total Solids) Long-chain polyol  5-30 10-20Crosslinking Agent 50-85 65-80 Short-chain polyol  3-30  5-25 Catalyst1.0-5.0 2.0-4.0 Coupling agent 0.1-2.0 0.15-0.8  Surfactant 0.01-5.0 0.1-1.0

In some exemplary embodiments, the binder composition is formulated tohave a reduced level of water soluble material post-cure as determinedby extracting water-soluble materials with deionized water for 2 hoursat room temperature using about 1000 g of deionized water per about 1gram of binder. The higher the level of water soluble material aftercure, the more likely it is that a cured material suffers from leachingif/when exposed to water and/or a hot/humid environment. In someexemplary embodiments, the binder composition has no greater than 6 wt.% of water soluble material after cure. In some exemplary embodiments,the binder composition has less than 5.0 wt. % water soluble materialafter cure, including less than 5.0 wt. %, 4.0 wt. %, 3.0 wt. %, lessthan 2.5 wt. %, less than 2.0 wt. %, less than 1.5 wt. %, or less than1.0 wt. %. It has been discovered that reducing the level of watersoluble material after cure to no greater than 6.0 wt. %, will improvethe tensile strength of the binder composition, as compared to anotherwise similar binder composition having greater than 6.0 wt. %,water soluble material after cure.

The amount of water soluble material remaining in the binder compositionafter cure may be determined at least in part by the amount ofcarboxylic acid groups in the binder. Particularly, excess acid groupsincrease the water-soluble content leads to an increase in water solublematerial post-cure. As shown in Table 3, below, Comparative Examples 1and 2 have COOH/OH ratios that are highly acidic, resulting in anunacceptably high percentage of water soluble material after cure. Incontrast, the percentage of water soluble material remaining after curedecreases substantially at COOH/OH ratios of 1/0.1 or less.

TABLE 3 Ambient Hot/humid Tensile/ tensile/ Water # PAA Sorbitol PVOHLOI LOI soluble % Set point ratio Comp. 52.17% 0     47.83% 37.9 38.3 4.90% COOH/OH = Ex. 1 1/1.5 (P/S = 1/0) Comp. 95.96% 0      4.04% 38.032.0 51.7% COOH/OH = Ex. 2 1/0.07(P/S = 1/0) Comp. 61.28% 38.72% 0    39.7 40.4  6.5% COOH/OH = Ex. 3 1/1.5(P/S = 0/1) Comp. 95.96%  4.04%0     44.3 38.7 15.9% COOH/OH = Ex. 4 1/0.1(P/S = 0/1) A 61.84% 27.51%10.65% 39.1 37.4  1.5% COOH/OH = 1/1.34(P/S = 0.21/0.79) B 61.84%  8.15%30.01% 39.5 38.8  2.6% COOH/OH = 1/1.11 (P/S = 0.72/0.28) C 66.39%27.51%  6.10% 39.8 39.6  1.9% COOH/OH = 1/1.13(P/S = 0.13/0.87) D 83.73%10.17%  6.10% 40.8 33.5  3.4% COOH/OH = 1/0.41(P/S = 0.29/0.71) E 71.51%16.30% 12.20% 40.0 38.8  4.6% COOH/OH = 1/0.82(P/S = 0.34/0.66) F 52.17%38.72%  9.11% 41.2 39.4  8.1% COOH/OH = 1/2.05(P/S = 0.14/0.86) G 83.73% 8.15%  8.12% 45.4 38.4  5.7% COOH/OH = 1/0.39(P/S = 0.41/0.59) H 91.52%0      0.84% 32.09 26.29 93.4% COOH/OH = 1/0.02(P/S = 1/0)

It has further been discovered that the total polyol content shouldcontain at least 10 wt. % of one or more short-chain polyols to producea binder composition with an acceptably low level (e.g., no greater than6 wt. %) of water soluble material after cure. This is particularlysurprising since generally, short-chain polyols, such as sorbitol, havehigh water solubility. Thus, it would be expected that increasing thelevel of sorbitol would increase the amount of water soluble material inthe binder composition.

In some exemplary embodiments, the binder composition has a viscosity ofless than about 400 cP at 30% solids or less, including less than about300 cP at 30% solids or less, and less than about 200 cP at 30% solidsor less. In various exemplary embodiments, the viscosity of the bindercomposition is no greater than 250 cP at 30% solids or less.

The fibrous products of the present disclosure comprise a plurality ofrandomly oriented fibers. In certain exemplary embodiments, theplurality of randomly oriented fibers are mineral fibers, including, butnot limited to glass fibers, glass wool fibers, mineral wool fibers,slag wool fibers, stone wool fibers, ceramic fibers, metal fibers, andcombinations thereof.

Optionally, other reinforcing fibers such as natural fibers and/orsynthetic fibers such as carbon, polyester, polyethylene, polyethyleneterephthalate, polypropylene, polyamide, aramid, and/or polyaramidfibers may be used in the non-woven fiber mats. The term “natural fiber”as used herein refers to plant fibers extracted from any part of aplant, including, but not limited to, the stem, seeds, leaves, roots, orphloem. Examples of natural fibers suitable for use as the reinforcingfiber material include wood fibers, cellulosic fibers, straw, woodchips, wood strands, cotton, jute, bamboo, ramie, bagasse, hemp, coir,linen, kenaf, sisal, flax, henequen, and combinations thereof. Nonwovenproducts may be formed entirely of one type of fiber, or they may beformed of a combination of types of fibers. For example, the insulationproducts may be formed of combinations of various types of glass fibersor various combinations of different inorganic fibers and/or naturalfibers depending on the desired application. In certain exemplaryembodiments the insulation products are formed entirely of glass fibers.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples illustrated belowwhich are provided for purposes of illustration only and are notintended to be all inclusive or limiting unless otherwise specified.

Example 1

Binder formulations with varying carboxylic acid/hydroxyl ratios andvarying polyvinyl alcohol/sorbitol ratios were utilized to form thinboards (425° F. cure temp and 0.125-inch thickness) that were cut intostrips. These ratios are depicted below in Table 5. Each board strip wassubjected to a 3-point bend test, wherein a load was placed in themiddle of each strip and the amount of load the board strip was able towithstand prior to break was measured. The results are depicted in FIG.1.

TABLE 4 Sample COOH/OH ratio PVOH/Sorbitol ratio 1a 1/0.1 0.1/0.9 1b1/0.1 0.5/0.5 1c 1/0.1 0.9/0.1 2a  1/0.66 0.1/0.9 2b  1/0.66 0.5/0.5 2c 1/0.66 0.9/0.1 3a 1/1.5 0.1/0.9 3b 1/1.5 0.5/0.5 3c 1/1.5 0.9/0.1

As illustrated in FIG. 1, within each carboxylic acid/hydroxyl groupratio, the flex stress/weight/LOI increased or decreased depending onthe polyvinyl alcohol/sorbitol ratio. Flex stress is a three-point bendtest (i.e., force until breakage) utilizing a 2″×6″ board with a ⅛″thickness. The highest flex stress/LOI overall was achieved when thecarboxylic acid/hydroxyl group ratio was 1/0.66. Moreover, within thisratio, the flex stress/LOI was further increased when the polyvinylalcohol/sorbitol ratio was 0.5/0.5. In fact, a polyvinylalcohol/sorbitol ratio of about 0.5/0.5 demonstrated the highest flexstress within each set of carboxylic acid/hydroxyl group ratios.

Example 2

Binder compositions with varying COOH/OH and long-chainpolyol/short-chain polyol ratios were utilized to form non-wovenfiberglass binder impregnated filter (BIF) sheets having a width of 9.5mm, thickness of 0.5 mm, and a length of 97 mm. The non-woven fiberglassBIF sheets were cured for 3 minutes and 30 seconds at 425° F. Thetensile strength, the Loss on Ignition (LOI) and tensile strengthdivided by the LOI (tensile strength/LOI) for each sample was determinedunder ambient conditions and steam (“hot/humid”) conditions. The tensilestrength was measured using Instron (Pulling speed of 2 inches/min). TheLOI of the reinforcing fibers is the reduction in weight experienced bythe fibers after heating them to a temperature sufficient to burn orpyrolyze the binder composition from the fibers. The LOI was measuredaccording to the procedure set forth in TAPPI T-1013 OM06, Loss onIgnition of Fiberglass Mats (2006). To create the hot/humid environment,the filter sheets were placed in an autoclave at 240° F. at a pressurebetween 400 and 500 psi for 60 minutes.

As illustrated in FIG. 2, the tensile/LOI appeared to generally increasein both ambient and hot/humid conditions when the ratio of short-chainpolyol in the composition was increased (within a COOH/OH ratio of1/0.1). This relationship appears consistent with the level of watersoubles remaining in the composition after cure. (FIG. 3). FIG. 3illustrates that as the ratio of short-chain polyol increases, thepercentage of water soluble materials in the composition after curedecreases.

These relationships continue when the COOH/OH ratio is adjusted to1/1.5, as illustrated in FIGS. 4 and 5. However, notably, the percentageof water soluble materials remaining in the composition after cure issubstantially lower at this COOH/OH range. For instance, even in acomposition lacking any short-chain polyol, the percentage water solublematerial is less than 8.0% and after some short-chain polyol is added,the percentage drops below 5.0%.

As the COOH/OH ratio is adjusted to 1/0.5, 1/0.1, and 1/1, however,although the percent water soluble material similarly declines withincreasing ratio of short-chain polyol, both the ambient and hot/humidtensile strengths remained relatively constant regardless of thelong-chain/short-chain polyol ratio. See FIGS. 6 through 9. It should benoted, however, that the highest ambient tensile strengths/LOI weredemonstrated at long-chain/short-chain polyol ratios of 0.5/0.5 and0.3/0.7, when the COOH/OH ratio was 1/0.5 (tensile strengths/LOI ofabout 44 and 45, respectively).

FIG. 10 illustrates the shift in tensile/LOI for filter sheetsimpregnated with binder compositions having varying COOH/OH ratios from1/0.1 to 1/10. As illustrated, the optimal tensile/LOI under bothambient and hot/humid conditions can be seen when the COOH/OH ratio isnot too low or too high. At both too high or too low COOH/OH ratios, thehot/humid tensile/LOI suffers, which leads to insufficient strengthproperties.

Example 3

Binder compositions with varying ratios were utilized to form fiberglassinsulation board (e.g., ceiling tiles). The insulation boards formedwith binder compositions according to the preset application (labeled asPAA/S/PVOH in various ratios of polyacrylic acid/sorbitol/polyvinylalcohol) were compared to boards formed using both a conventionalcarbohydrate-based binder composition (“Starch-Hybrid Binder Board”) anda phenol urea formaldehyde binder composition (“PUF Board”). The elasticmodulus, compressive strength (delta b), and sag (inches) for eachsample was determined under ambient conditions.

As illustrated in FIG. 11, each of the PAA/S/PVOH insulation boardsamples demonstrated improved Flexural Elastic Modulus, as compared toboth conventional carbohydrate-based binder compositions and phenol ureaformaldehyde-based binder compositions. PAA/S/PVOH 50:20:30 andPAA/S/PVOH 60:10:30 demonstrated the greatest improvement, with FlexuralElastic Modulus levels at about 70 psi and 68 psi, respectively. Incontrast, the PUF Board demonstrated a Flexural Elastic Modulus of about46 psi and the Starch-Hybrid Binder Board demonstrated an elasticmodulus of about 31 psi. In some exemplary embodiments, an insulationboard with a thickness of about 1 inch and a density of about 6 lbs/ft³according to the present inventive concepts achieves an elastic modulusof at least 40 psi, including at least 45 psi, at least 50 psi, and atleast 55 psi.

FIG. 12 illustrates the sag observed by various 4′×4′ insulation boardpanels after a set number of days in a hot/humid environment at 90 F/90%rH (relative humidity).

As shown in FIG. 12, the PAA/S/PVOH binder compositions having lowerlevels of PVOH (i.e., PAA/S/PVOH 60:20:15 and PAA/S/PVOH 75:10:15)demonstrated less sag under hot/humid conditions than both PUF Board andStarch-Hybrid Binder Board. This indicates that lowering the long-chainpolyol in the binder compositions may help improve the hot/humidperformance in applications that need very high standard of hot andhumid performances.

FIG. 13 illustrates the compressive strength at 10% deformation offiberglass board products of different binders and LOI %. The test wasperformed on 6″×6″ insulation boards, with a thickness about 1″ anddensity about 6 lb/ft², according to ASTM method C-165. As illustratedin FIG. 13, the compressive strength of the insulation boards formedwith a PAA/S/PVOH binder exceeded that of insulation boards formed withboth a starch-hybrid binder and a PUF binder, demonstrating compressivestrengths of about 260 lbs/ft² to over 500 lbs/ft². In some exemplaryembodiments, a 6″×6″ insulation board with a thickness of about 1 inchaccording to the present inventive concepts achieves a compressivestrength of at least 200 lbs/ft², including at least 300 lbs/ft², atleast 400 lbs/ft², and at least 500 lbs/ft².

FIG. 14 illustrates the bond strength at break of fiberglass boardproducts of different binders and LOI %. The test measures the strengthin Z direction of 6″×6″ insulation boards with a thickness of about 1″and density of about 6 lb/ft². As illustrated in FIG. 14, the bondstrength of insulation boards formed with PAA/S/PVOH binders exceededthat of insulation board formed with a starch-hybrid binder.Additionally, the insulation boards formed with PAA/S/PVOH bindersdemonstrated a comparable bond strength to insulation boards formed witha PUF binder, demonstrating bond strengths of about 10 lbs/ft² to over15 lbs/ft². In some exemplary embodiments, a 6″×6″ insulation board witha thickness of about 1 inch according to the present inventive conceptsachieves a bond strength of at least 7.5 lbs./ft²/LOI, including atleast 10 lbs./ft²/LOI, at least 12.5 lbs./ft²/LOI, and at least 15lbs./ft²/LOI.

It will be appreciated that many more detailed aspects of theillustrated products and processes are in large measure, known in theart, and these aspects have been omitted for purposes of conciselypresenting the general inventive concepts. Although the presentinvention has been described with reference to particular means,materials and embodiments, from the foregoing description, one skilledin the art can easily ascertain the essential characteristics of thepresent disclosure and various changes and modifications can be made toadapt the various uses and characteristics without departing from thespirit and scope of the present invention as described above and setforth in the attached claims.

What is claimed is:
 1. An aqueous binder composition comprising: along-chain polyol having at least two hydroxyl groups and a numberaverage molecular weight of at least 2,000 Daltons; greater than 65 wt.% of a cross-linking agent comprising at least two carboxylic acidgroups; and a short-chain polyol having at least two hydroxyl groups anda number average molecular weight less than 2,000 Daltons; wherein aratio of long-chain polyol to short-chain polyol is from 0.1/0.9 to0.9/0.1, and wherein the wt. % is based on the total solids content ofthe aqueous binder composition.
 2. The aqueous binder composition ofclaim 1, wherein the cross-linking agent comprises a polymericpolycarboxylic acid.
 3. The aqueous binder composition of claim 1,wherein the cross-linking agent comprises a homopolymer of copolymer ofacrylic acid.
 4. The aqueous binder composition of claim 1, wherein thecross-linking agent comprises polyacrylic acid.
 5. The aqueous bindercomposition of claim 1, wherein the cross-linking agent is present inthe binder composition in an amount of from greater than 65 wt. % to 80wt. %, based on the total solids content of the aqueous bindercomposition.
 6. The aqueous binder composition of claim 1, wherein thelong-chain polyol is selected from the group consisting of polyvinylalcohol and polyvinyl acetate.
 7. The aqueous binder composition ofclaim 1, wherein the long-chain polyol is present in the bindercomposition in an amount up to 30 wt. %, based on the total solidscontent of the aqueous binder composition.
 8. The aqueous bindercomposition of claim 1, wherein the short-chain polyol comprises one ormore of a sugar alcohol, 2,2-bis(methylol)propionic acid,tri(methylol)propane, and a short-chain alkanolamine.
 9. The aqueousbinder composition of claim 8, wherein the short-chain polyol comprisesa sugar alcohol selected from the group consisting of glycerol,erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol,isomaltitol, lactitol, cellobitol, palatinitol, maltotritol, syrupsthereof, and mixtures thereof.
 10. The aqueous binder composition ofclaim 9, wherein the short-chain polyol comprises sorbitol.
 11. Theaqueous binder composition of claim 1, wherein the ratio of long-chainpolyol to short-chain polyol is between 0.3/0.7 and 0.7/0.3.
 12. Theaqueous binder composition of claim 1, wherein the short-chain polyol ispresent in the binder composition in an amount from 3 wt. % to 30 wt. %,based on the total solids content of the aqueous binder composition. 13.The aqueous binder composition of claim 1, wherein: the long-chainpolyol comprises polyvinyl alcohol; the cross-linking agent comprisespolyacrylic acid; and the short-chain polyol comprises sorbitol.
 14. Anaqueous binder composition comprising: a long-chain polyol having atleast two hydroxyl groups and a number average molecular weight of atleast 2,000 Daltons; a cross-linking agent comprising a polymericpolycarboxylic acid; and a short-chain polyol having at least twohydroxyl groups and a number average molecular weight less than 2,000Daltons; wherein a ratio of long-chain polyol to short-chain polyol isfrom 0.1/0.9 to 0.9/0.1, and wherein the wt. % is based on the totalsolids content of the aqueous binder composition.
 15. The aqueous bindercomposition of claim 14, wherein the cross-linking agent consists ofpolyacrylic acid.
 16. The aqueous binder composition of claim 15,wherein the cross-linking agent is present in the binder composition inan amount from 50 wt. % to 85 wt. %, based on the total solids contentof the aqueous binder composition.
 17. The aqueous binder composition ofclaim 14, wherein the long-chain polyol is present in the bindercomposition in an amount up to 30 wt. %, based on the total solidscontent of the aqueous binder composition.
 18. The aqueous bindercomposition of claim 14, wherein the short-chain polyol is present inthe binder composition in an amount from 3 wt. % to 30 wt. %, based onthe total solids content of the aqueous binder composition.
 19. Aninsulation product comprising: a plurality of randomly oriented fibers;and the aqueous binder composition of claim 1 at least partially coatingthe fibers.
 20. An insulation product comprising: a plurality ofrandomly oriented fibers; and the aqueous binder composition of claim 14at least partially coating the fibers.